Ether diamines quaternaries

ABSTRACT

The present invention is related to a series of derivatives of novel ether diamine compounds prepared by the cynobutylation reaction of an alcohol having 3 to 22 carbon atoms with 2-pentenenitrile to form a branched alkyl ether nitrile. The etheraminonitriles formed by the process are hydrogenated to form alkylether amines. The resulting product can be reacted with 2-pentenenitrile and or acrylonitrile and in subsequent step, hydrogenated to yield a diamine. Specifically, the present invention deals with two types of tertiary amines one made by the reaction of novel ether diamines compounds with ethylene oxide, propylene oxide or butylene oxide or mixtures thereof, producing alkoxylated tertiary amines and the other made by the reaction of novel ether amine compounds with formaldehyde and hydrogen producing methylated tertiary amines. The invention also disclosed novel amine oxides, and quaternary compounds made from said tertiary amines.

RELATED APPLICATION

This application is a divisional application of Ser. No. 09/722,197filed Nov. 27, 2000, which in turn is a continuation in part ofapplication Ser. No. 09/459,562 filed Dec. 13, 1999, now U.S. Pat. No.6,114,585 issued September 2000, which is a continuation in part ofapplication Ser. No. 09/566,505 filed May 8, 2000, now U.S. Pat. No.6,331,648 issued December 2001.

FIELD OF THE INVENTION

The present invention relates to a series of derivatives of novel etherdiamine compounds prepared by the cyanobutylation reaction of an alcoholhaving 3 to 22 carbon atoms with 2-pentenenitrile to form a branchedalkyl ether nitrile. The alkyl ether nitriles formed by the process arehydrogenated to form alkylether amines. The resulting products are thenreacted with 2-pentenenitrile or acrylonitrile and hydrogenated to yielda diamine, which can likewise be derivatized. Specifically, the presentinvention deals with two types of tertiary amines, one made by thereaction of novel ether diamines compounds with ethylene oxide,propylene oxide, butylene oxide or mixtures thereof producingalkoxylated tertiary diamines and the other conveniently made by thereaction of novel ether diamine compounds with formaldehyde and hydrogenproducing methylated tertiary diamines. The invention also disclosesnovel diamine oxides, and quaternary compounds made from said tertiaryamines.

BACKGROUND OF THE INVENTION

U.S. Pat. Nos. 4,260,556 and 4,211,725 teach reaction of2-pentenenitrile with ammonia or ethylenediamine to producealkylaminonitriles. U.S. Pat. No. 4,496,474 teaches the reaction of2-pentenenitrile with alkylamines having from 8 to 22 carbons to producethe corresponding nitrile compound. U.S. Pat. No. 5,070,202 teaches aprocess having improved reaction rate and selectivity in the reaction of2-pentenenitrile with amines to form alkylaminonitriles by theincorporation of from 15 to 60 weight percent water in the reactionmixture. These references do not include the critical ether linkageneeded to make the products of the present invention.

U.S. Pat. No. 5,902,883 to Herkes discloses the cyanobutylation ofvarious amines to make diamines. Herkes uses 3-pentenenitrile,4-pentenenitrile or mixtures of 3-pentenenitrile and 4-pentenenitrile tomake his product. This does not result in the desired branching thatcomes from the compounds of the present invention, nor does it includethe critical ether linkage in the molecule. Herkes has done some workwith the cyanobutylation of lower molecular weight alcohols (C3 to C8)to form primary amines. These materials lack the hydrophobicity to begood surface-active agents.

It has now been found that by reacting alcohols with 2-pentenenitrileand hydrogenating to the alkyloxypentyl amines, followed bycyonoethylation or cyonobutylation to form diamines, followed byalkoxylation or methylation to form tertiary amines and in a subsequentstep derivitization of said tertiary amines results in products withunique properties. Further reaction to form the salts, quaternary salts,or amine oxides also result in products with unique properties. Theseinclude (a) superior liquidity of the resulting products, (b) improvedsurfactant properties and (c) improved solubility. All of these willbecome clear as one reads the teachings of the present invention.

SUMMARY OF THE INVENTION

The present invention relates to a series of derivatives of novel etherdiamine compounds prepared by the cyanobutylation reaction of an alcoholhaving 3 to 22 carbon atoms with 2-pentenenitrile to form a branchedalkyl ether nitrile. The alkyl ether nitrites formed by the process arehydrogenated to form alkylether amines. The ether amine compounds may beused as raw materials for the preparation of the derivatives of thecurrent invention which are the topic of application Ser. No. 459,562filed Dec. 13, 1999, now U.S. Pat. No. 6,114,585 issued September 2000,and application Ser. No. 09/566,505 filed May 8, 2000 incorporatedherein by reference. The resulting product can be reacted with2-pentenenitrile and or acrylonitrile and in a subsequent step,hydrogenated, to yield a diamine. Specifically, the present inventiondeals with two types of tertiary amines. One made by the reaction ofnovel ether diamine compounds with ethylene oxide, propylene oxide,butylene oxide or mixtures thereof to produce an alkoxylated tertiarydiamine, and the other conveniently made by the reaction of novel etherdiamine compounds with formaldehyde and hydrogen to produce a methylatedtertiary diamine. The invention also discloses novel amine oxides, aminesalts and quaternary compounds made from said tertiary diamines.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a series of derivatives of novel etherdiamine compounds prepared by the cyanobutylation reaction of an alcoholhaving 3 to 22 carbon atoms with 2-pentenenitrile to form a branchedalkyl ether nitrile. The etheraminonitriles formed by the process arehydrogenated to form alkyl ether amines. The resulting product can bereacted with 2-pentenenitrile or acrylonitrile and hydrogenated to yielda diamine. Specifically, the present invention deals with two types oftertiary amines, one made by the reaction of novel ether diaminecompounds with ethylene oxide, propylene oxide or butylene oxide ormixtures thereof producing alkoxylated tertiary diamines and the othermade by the reaction of novel ether diamine compounds with formaldehydeand hydrogen producing methylated tertiary diamines. The tertiary etherdiamines are also converted to amine oxides and quaternaries.

The compounds of the present invention are diamines and derivativesfalling into the following classes:

Class 1

A branched ether diamine conforming to the following structure:

wherein;

e is 0 or 1;

R¹ is selected from the group consisting of alkyl having 3 to 22 carbonatoms;

R² is —(CH₂CH₂O)_(a)—(CH₂CH(CH₃)O)_(b)—(CH₂CH(CH₂CH₃)O)_(c)—;

a, b and c are independently integers ranging from 0 to 30;

R³ is

d is 1.

Class 2

An alkoxylated tertiary ether diamine conforming to the followingstructure:

wherein;

R¹ is selected from the group consisting of alkyl having 3 to 22 carbonatoms, aryl having 6 to 20 carbon atoms;

R² is —(CH₂CH₂O)_(a)(CH₂CH(CH₃)O)_(b)—(CH₂ CH(CH₂CH₃)O)_(c)—;

a, b and c are independent integers ranging from 0 to 30, with theprovision that a+b+c are a minimum of 0 and a maximum of 60;

R³ is

d is 1;

e is 0 or 1;

x, y and z are integers ranging from 0 to 30 with the provision thatx+y+z is a minimum of 2 and a maximum of 60.

Class 3

An alkoxylated tertiary ether diamine oxide conforming to the followingstructure:

wherein;

R¹ is selected from the group consisting of alkyl having 3 to 22 carbonatoms, aryl having 6 to 20 carbon atoms;

R² is —(CH₂CH₂O)_(a)—(CH₂CH(CH₃)O)_(b)—(CH₂CH(CH₂CH₃)O)_(c)—;

a, b and c are independent integers ranging from 0 to 30, with theprovision that a+b+c are a minimum of 0 and a maximum of 60;

R³ is

d is 1;

e is 0 or 1;

x, y and z are integers ranging from 0 to 30 with the provision thatx+y+z is a minimum of 2 and a maximum of 60.

Class 4

A trimethyl tertiary ether diamine conforming to the followingstructure:

wherein;

R¹ is selected from the group consisting of alkyl having 3 to 22 carbonatoms, aryl having 6 to 20 carbon atoms;

R² is —(CH₂CH₂O)_(a)—(CH₂CH(CH₃)O)_(b)—(CH₂CH(CH₂CH₃)O)_(c)—;

a, b and c are independent integers ranging from 0 to 30, with theprovision that a+b+c are a minimum of 0 and a maximum of 60;

R³ is

d is 1;

e is 0 or 1.

Class 5

A trimethyl tertiary ether diamine oxide conforming to the followingstructure:

wherein:

R¹ is selected from the group consisting of alkyl having 3 to 22 carbonatoms, aryl having 6 to 20 carbon atoms;

R² is —(CH₂CH₂O)_(a)—(CH₂CH(CH₃)O)_(b)—(CH₂CH(CH₂CH₃)O)_(c)—;

a, b and c are independent integers ranging from 0 to 30, with theprovision that a+b+c are a minimum of 0 and a maximum of 60;

R³ is

d is 1;

e is 0 or 1.

Class 6

An ether diamine quaternary conforming to the following structure:

wherein:

R¹ is selected from the group consisting of alkyl having 3 to 22 carbonatoms;

R² is —(CH₂CH₂O)_(a)—(CH₂CH(CH₃)O)_(b)—(CH₂CHCH₂CH₃)O)_(c)—;

a, b and c are independent integers ranging from 0 to 30;

R³ is

d is 1;

e is 0 or 1;

R⁴ and R⁵ are selected from the group consisting of —CH₃ and—(CH₂CH₂O)_(x)—(CH₂CH(CH₃)O)_(y)—(CH₂CH(CH₂CH₃)O)_(z)H;

x, y and z are independent integers ranging from 0 to 20, with theprovision that x+y+z is greater than or equal to 3;

R⁶ is selected from the group consisting of —CH₃ and —CH₂—C₆ H₅

M is an appropriate anion needed for charge balance such as Cl, Br, andCH₃SO₄, etc.

Each of the various classes of compounds has in common the fact thatthey are derivatives of a penetene nitrile diamine. The preparation ofthe compounds of the present invention includes the following steps: (1)reaction of an ether amine with pentene nitrile or acrylonitrilefollowed by (2) hydrogenation of the nitrile to the diamine, followed by(3) reaction with either formaldehyde and hydrogen or alkoxylated toform a tertiary ether diamine then (4) derivatization of the tertiaryamine into an amine oxide or quaternary compound.

Preferred Embodiments

In a preferred embodiment of the branched ether diamine conforming tothe following structure:

wherein;

e is 0 or 1;

R¹ is selected from the group consisting of alkyl having 3 to 22 carbonatoms;

R² is —(CH₂CH₂O)_(a)—(CH₂CH(CH₃)O)_(b)—(CH₂CH(CH₂CH₃)O)_(c)—;

a, b and c are independently integers ranging from 0 to 30;

R³ is

d is 1;

R¹ is C₁₂H₂₅,

a, b and c are each 0, d is 1 and e is 1.

In another preferred embodiment of the branched ether diamine R¹ ishydrogenated tallow, a, b and c are each 0, and e is 0.

In still another preferred embodiment of the ether diamine R¹ is C₁₂H₂₅,a, b and c are each 0, and e is 0.

In a preferred embodiment of the branched ether diamine, R¹ ishydrogenated tallow, a, b and c are each 0, and e is 0.

In a preferred embodiment of the alkoxylated tertiary ether diamineconforming to the following structure:

wherein;

R¹ is selected from the group consisting of alkyl having 3 to 22 carbonatoms, aryl having 6 to 20 carbon atoms;

R² is —(CH₂CH₂O)_(a)—(CH₂CH(CH₃)O)_(b)—(CH₂ CH(CH₂CH₃)O)_(c)—;

a, b and c are independent integers ranging from 0 to 30, with theprovision that a+b+c are a minimum of 0 and a maximum of 60;

R³ is

d is 1;

e is 0 or 1;

x, y and z are integers ranging from 0 to 30 with the provision thatx+y+z is a minimum of 2 and a maximum of 60; R¹ is C₁₂H₂₅, a, b, and ceach 0, x is 5, and e is 1.

In another preferred embodiment of the alkoxylated tertiary etherdiamine R¹ is C₁₃H₂₇, a is 0, b is 0, c is 30, y is 2, d is 1 and e is1.

In another preferred embodiment of the alkoxylated tertiary etherdiamine R¹ is C₁₂H₂₅, a, b, and c each 0, x is 5, and e is 0.

In still another preferred embodiment of the alkoxylated tertiary etherdiamine R¹ is C₁₃H₂₇, a is 0, b is 0, c is 30, y is 2, and e is 0.

A preferred embodiment of the alkoxylated tertiary ether diamine oxideconforming to the following structure:

wherein;

R¹ is selected from the group consisting of alkyl having 3 to 22 carbonatoms, aryl having 6 to 20 carbon atoms;

R² is —(CH₂CH₂O)_(a)—(CH₂CH(CH₃)O)_(b)—(CH₂CH(CH₂CH₃)O)_(c)—;

a, b and c are independent integers ranging from 0 to 30, with theprovision that a+b+c are a minimum of 0 and a maximum of 60;

R³ is

d is 1;

e is 0 or 1;

x, y and z are integers ranging from 0 to 30 with the provision thatx+y+z is a minimum of 2 and a maximum of 60 is when R¹ is C₁₀H₂₁, a, band c are each 0, x is 60, and e is 1.

In another preferred embodiment of the alkoxylated tertiary diamineoxide R¹ is C₈H₁₇, a is 1, b is 30, c is 2, x is 1 and y is 2, and e is1.

In another preferred embodiment of the alkoxylated tertiary diamineoxide R¹ is C₁₀H₂₁, a, b and c are each 0, x is 60, and e is 0.

In still another preferred embodiment of the alkoxylated tertiarydiamine oxide of R¹ is C₈H₁₇, a is 1, b is 30, c is 2, x is 1 and y is2, and e is 0.

In a preferred embodiment of the trimethyl tertiary ether diamineconforming to the following structure:

wherein;

R¹ is selected from the group consisting of alkyl having 3 to 22 carbonatoms, aryl having 6 to 20 carbon atoms;

R² is —(CH₂CH₂O)_(a)—(CH₂CH(CH₃)O)_(b)—CH₂CH(CH₂CH₃)O)_(c)—;

a, b and c are independent integers ranging from 0 to 30, with theprovision that a+b+c are a minimum of 0 and a maximum of 60;

R³ is

d is 1;

e is 0 or 1 is when R¹ is C₃H₇, b is 5, and e is 1.

In another preferred embodiment of the trimethyl tertiary ether diamineR¹ is C₁₂H₂₅, a is 30, and e is 1.

In another preferred embodiment of the trimethyl tertiary ether diamineR¹ is C₃H₇, b is 5, and e is 1.

In another preferred embodiment of the trimethyl tertiary ether diamineR¹ is C₁₂H₂₅, a is 30, and e is 1.

A preferred embodiment of the trimethyl tertiary ether diamine oxideconforming to the following structure:

wherein:

R¹ is selected from the group consisting of alkyl having 3 to 22 carbonatoms, aryl having 6 to 20 carbon atoms;

R² is —(CH₂CH₂O)_(a)—(CH₂CH(CH₃)O)_(b)—CH₂CH(CH₂CH₃)O)_(c)—;

a, b and c are independent integers ranging from 0 to 30, with theprovision that a+b+c are a minimum of 0 and a maximum of 60;

R³ is

d is 1;

e is 0 or 1 is when R¹ is C₈H₁₇, a is 1, b is 30, c is 2, and e is 1.

Another preferred embodiment of the trimethyl tertiary ether diamine iswhen R¹ is C₁₀H₂₁, a, b and c are each 0, and e is 0.

In a preferred embodiment of ether diamine quaternary conforming to thefollowing structure:

wherein:

R¹ is selected from the group consisting of alkyl having 3 to 22 carbonatoms;

R² is —(CH₂CH₂O)_(a)—(CH₂CH(CH₃)O)_(b)—(CH₂CHCH₂CH₃)O)_(c)—;

a, b and c are independent integers ranging from 0 to 30;

R³ is

d is 1;

e is 0 or 1;

R⁴ and R⁵ are selected from the group consisting of —CH₃; and

—(CH₂CH₂O)_(x)—(CH₂CH(CH₃)O)_(y)—(CH₂CH(CH₂CH₃)O)_(z)H;

x, y and z are independent integers ranging from 0 to 20, with theprovision that x+y+z is greater than or equal to 3;

R⁶ is selected from the group consisting of —CH₃ and —CH₂—C₆ H₅;

M is an appropriate anion needed for charge balance such as Cl, Br, andCH₃SO₄, is when R¹ is hydrogenated tallow, a, b and c are each 0, R⁴ andR⁵ and R⁶ are CH₃ and M is Cl, and e is 0.

Another preferred embodiment of the ether diamine quaternary R¹ is C₃H₇,b is 5,

R⁴, R⁵ and R⁶ are CH₃.

Raw Material Amine Preparation

The ether amine compounds used as raw materials for the preparation ofthe derivatives of the current invention are the topic of applicationSer. No. 459,562 filed Dec. 13, 1999, now U.S. Pat. No. 6,114,585 issuedSeptember 2000, and application Ser. No. 09/566,505 filed May 8, 2000incorporated herein by reference. They conform to the followingstructure;

R¹ is selected from the group consisting of alkyl having 3 to 22 carbonatoms,

R² is —(CH₂CH₂O)_(a)—(CH₂CH(CH₃)O)_(b)—(CH₂CH(CH₂CH₃)O)_(c)—;

a, b and c are independently integers ranging from 0 to 30,

R³ is

d is 0 or 1.

Class 1: Ether Monoamine (d=0)

The ether monoamines conform to the following structure:

wherein;

R¹ is selected from the group consisting of alkyl having 3 to 22 carbonatoms

R² is —(CH₂CH₂O)_(a)—(CH₂CH(CH₃)O)_(b)—(CH₂CH(CH₂CH₃)O)_(c)—;

a, b and c are independently integers ranging from 0 to 30,

R³ is

d is 0.

Ether Diamine (d=1)

Ether diamine compounds of the present invention conform to thefollowing structure:

e is 0 or 1;

R¹ is selected from the group consisting of alkyl having 3 to 22 carbonatoms

R² is —(CH₂CH₂O)_(a)—(CH₂CH(CH₃)O)_(b)—(CH₂CH(CH₂CH₃)O)_(c)—;

a, b and c are independently integers ranging from 0 to 30,

R³ is

d is 1.

RAW MATERIALS ALCOHOLS

The alcohols and alcohol alkoxylates used in the manufacture of theproducts of the present invention are well known in the art and arecommercially available from a variety of suppliers. Suppliers of thesematerials include Shell Chemical Company, Condea-Vista, Exxon ChemicalCompany, Henkel Corporation and Siltech Corporation.

R¹OR²—H

Where R² is (CH₂CH₂O)_(a)—(CH₂CH(CH₃)O)_(b)—(CH₂CH(CH₂CH₃)O)_(c)

R² Example R¹ a b c 1 C₁₂H₂₅ 0 0 0 2 C₃H₇ 0 5 0 3 C8H17 0 0 0 4 C₁₀H₂₁ 00 0 5 C₁₃H₂₇ 0 0 0 6 Hydrogenated Tallow 0 0 0 40% C₁₆H₃₃ & 60% C₁₈H₃₇ 7Behenyl 30% C₂₀H₄₁ & 0 0 0 70% C₂₂H₄₅ 8 C₁₂H₂₅ 30  0 0 9 C₈H₁₇ 1 30  210  C₁₃H₂₇ 0 0 30 

Procedure Preparation of Ether Nitrile (Cyanobutylation)

One mole of base alcohol is charged to a reaction flask and one moleplus approximately 10% excess of the 2-pentenenitrile is placed in anaddition flask. Material is heated while stirred to a temperature ofabout 40° C. Base catalyst (KOH) is added based on the total weight ofthe reactants charged at about a 0.1 to 0.5% or more preferably 0.2-0.3%basis. A nitrogen blanket is applied to the headspace of the reactionvessel and the mixture is stirred for about 15 minutes at 40° C. toincorporate the catalyst into the alcohol. Keep the reaction flaskheadspace blanketed with nitrogen throughout the entire reaction period.

The addition of the 2-pentenenitrile is exothermic. Charge the2-pentenentrile to the reaction vessel such that the temperature ofreaction is maintained at 40-65° C., more preferably 45-60° C., and mostpreferably 50-55° C. When all of the 2-pentenenitrile has been added letreact for 2 hours at 50° C. After the 2 hours add an equivalent amountof acid to neutralize the base catalyst. Stir mixture for 15 minutesthen filter the 3-alkoxy-3-ethylpropylnitrile to be hydrogenated toremove salts formed on neutralization of the KOH.

Hydrogenation of 3-Alkoxy-3 Ethylpropylnitrile

Charge the ether nitrile to an autoclave that is capable of operating atpressures up to 600 psig. Charge 2% by weight of Raney® Nickel (basedupon the weight of the alcohol to the vessel). Seal autoclave and startagitation, increase heat to about 80 to 100° C. and vacuum strip out anywater that may have been introduced during cyanobutylation or fromRaney® nickel. When no more water appears on the condenser of the vacuumset-up, close autoclave and charge hydrogen gas to about 5 psig. Chargeammonia to vessel to about 60 to 70 psig. Increase heat to 135° C. andnote pressure. Add hydrogen such that about 150 to 200 psig additionalpressure is measured on the autoclave pressure gauge. Maintaincontinuous hydrogen addition in this manner for a period of 4-6 hours,then close the hydrogen inlet valve and note pressure on the pressuregauge.

Turn off heat and cool to about 70° C. Carefully, open vent to releasepressure and vacuum strip to remove ammonia. Discharge the3-alkoxy-3ethylpropylamine and filter to remove Raney® nickel catalyst.

EXAMPLE 11 Preparation of 3-Dodecyloxy-3-ethylpropylnitrile(Cyanobutylation)

To a 500 ml round bottomed flask fitted with a mechanical stirrer, gasinlet tube and dropping funnel was added 186 g (1 mole) of n-dodecylalcohol (Example 1) and 0.7 g of KOH. A nitrogen blanket was maintainedthroughout the procedure. The temperature was increased to 40° C. whilestirring to dissolve and disperse the KOH. The dropping funnel wascharged with 90.0 g of 2-pentenenitrile (1.11 mole). The nitrile wasadded with stirring at a rate that kept the reaction temperature fromrising over 50° C. After the addition the reaction was allowed toproceed for an additional 2 hours at 50° C. The catalyst, KOH, was thendeactivated by neutralization with an equivalent amount of acetic acid.After neutralization the mixture was stirred for 15 minutes and thenfiltered to remove the salts that formed on neutralization. The excess2-pentenenitrile was then removed by vacuum stripping.

EXAMPLES 12-20

Example 11 is repeated, only this time replacing the alcohol examplewith the type and quantity of alcohol shown.

Ether nitrile Alcohol KOH (95%) Example Example Grams Grams 12 2 350.01.0 13 3 130.0 0.5 14 4 158.0 0.5 15 5 200.0 0.6 16 6 259.0 0.7 17 7318.0 0.8 18 8 1506.0  3.8 19 9 2054.0  5.0 20 10  2360.0  6.0

EXAMPLE 21 Preparation 3-Dodecyloxy-3-ethylpropylamine (Hydrogenation)

Then 265 grams (0.99 mole) of 3-dodecyloxy-3-ethylpropylnitrile waspoured into a suitable sized autoclave equipped with stirring. Raney®nickel, 5.3 g was also added. After sealing the autoclave and heating to80° C. a vacuum was applied while stirring to remove water introducedwith the catalyst. When no more water appeared on the condenser of thevacuum set-up the vacuum was released and hydrogen was allowed to fillthe vessel to a pressure of 5 psig. Ammonia was then added until thepressure rose to 65 psig. The temperature was then increased to 135° C.that caused the pressure to rise to about 150 psig. The pressure wasthen increased to 400 psig with hydrogen and the stirring speedincreased to 1200 rpm. After 4 hours the valve to the hydrogen cylinderwas closed and the pressure in the headspace monitored. Since thepressure dropped by 100 psig over the next 15 minutes, the valve wasopened again and the reaction allowed to proceed for another hour. Afterchecking for a pressure drop again, none was noted over the next 15minutes and the reaction was declared complete. The heat was turned offand cooling water run through the coils until the temperature dropped to70° C. After venting off the hydrogen and flushing with nitrogen,residual ammonia was vacuum stripped. The product,3-n-dodecyloxy-3ethylpropylamine, was filtered to remove Raney® nickelcatalyst. The yield was essentially quantitive.

Example 21 is repeated, only this time replacing the ether mononitrileof example 12 with the type and quantity shown.

Ether Mono Amine Ether Nitrile Example Example Grams 22 12 435.0 23 13215.0 24 14 243.0 25 15 285.0 26 16 344.0 27 17 403.0 28 18 1591.0  2919 2139.0  30 20 2445.0 

The products are used to prepare ether diamines and their derivativesthat are the subject of this invention.

Class 2: Ether Diamine (d is 1)

Procedure

The products of class 1 are reacted with additional 2-pentenenitrile andor acrylonitrile to make the either aminonitrile, then subsequentlyreacted with hydrogen to make the ether diamine.

EXAMPLES 31-35 ARE ETHER DIAMINES WHERE D IS 1 AND E IS 1 EXAMPLE 31Preparation of 3-Dodecyloxy-3-ethylpropylamine Pentenenitrile(Cyanobutylation of Ether Mono Amine)

To a suitable reaction flask is added 275.0 grams of3-dodecyloxy-3-ethylpropyl amine (example 21). Heat while underagitation to 40° C. A nitrogen blanket is applied to the headspace ofthe reaction vessel. Keep the reaction flask headspace blanketed withnitrogen throughout the entire reaction period. Begin addition of 90.0grams of 2-pentenenitrile under good agitation keeping the temperaturebelow 50° C. When all of the 2-pentenenitrile has been added, let reactfor two hours at 50° C.

Preparation of Diamine (Hydrogenation)

Charge the etheramine pentenenitrile as prepared to an autoclave that iscapable of operating at pressures up to 600 psig. Autoclave must beplaced in a hood or vented area and must be equipped with vacuumstripping, cooling, and heating. Carefully charge a known quantity ofmetal catalyst such as Raney Nickel to the vessel. Use 2% by weightbased upon the weight of the total batch. Seal autoclave and startagitation, increase heat to about 80 to 100° C. and vacuum strip out anywater that may have been introduced during cyanobutylation or from theRaney® Nickel. When no more water appears on the condenser of the vacuumset-up, close autoclave and charge hydrogen gas to about 5 psig. Chargeammonia to vessel up to about 60 to 70 psig. Increase heat to 135° C.and note pressure. Add hydrogen such that about 150 to 200 psigadditional pressure is measured on the autoclave pressure gauge.Maintain this increase with hydrogen gas that will be rapidly taken upby the reaction mixture during the first hour of the reaction. Maintaincontinuous hydrogen addition in this manner for a period of 4 to 6hours. After this time, close the valve from the hydrogen to theautoclave and note pressure on pressure gauge. If pressure is stable anddoes not decrease after 15 minutes, reaction is complete. Otherwise,continue adding hydrogen as previously described for one hour and thenre-check.

Example 31 is repeated, only this time replacing the ether monoamine ofexample 31 with the type and quantity of monoether amine shown below:

Ether Diamine Ether Monoamine Example Example Grams 32 22 440.0 33 23220.0 34 24 248.0 35 25 290.0

EXAMPLES 36-40 ARE OTHER DIAMINES WHERE d IS 1 AND e IS ZERO EXAMPLE 36Preparation of Tallowoxyethypropylamine Propylnitrile (Cyanoethylationof Ether Mono Amine)

To a suitable reaction flask is added 349 grams oftallowoxyethylpropylamine (example 26). Heat while under agitation to40° C. A nitrogen blanket is applied to the headspace of the reactionvessel. Keep the reaction flask headspace blanketed with nitrogenthroughout the entire reaction period. Begin addition of 60 grams ofacrylonitrile under good agitation keeping the temperature below 50° C.When all of the acrylonitrile has been added, let react for two hours at50° C.

Preparation of Diamine (Hydrogenation)

Charge the etheramine propylnitrile as prepared to an autoclave that iscapable of operating at pressures up to 600 psig. Carefully charge knownquantity of metal catalyst such as Raney® Nickel to the vessel. Use 2%by weight of the total batch. Seal autoclave and start agitation,increase heat to about 80 to 100° C. and vacuum strip out any water thatmay have been introduced during cyanoethylation or from the Raney®Nickel. When no more water appears on the condenser of the vacuum setup,close autoclave and charge hydrogen gas to about 5 psig. Charge ammoniato vessel up to about 60-70 psig. Increase heat to 135° C. and notpressure. Add hydrogen such that about 150-200 psig. Additional pressureis measured on the autoclave pressure gauge. Maintain this increase withhydrogen gas that will be rapidly taken up by the reaction mixtureduring the first hour of the reaction. Maintain continuous hydrogenaddition in this manner for a period of 4-6 hours. After this time,close the valve from the hydrogen to the autoclave and note pressure onpressure gauge. If pressure is stable and does not decrease after 15minutes, reaction is complete. Otherwise, continue adding hydrogen aspreviously described for one hour and then re-check.

Example 36 is repeated, only this time replacing the etheramine ofexample 36 with the type and quantity of monoetheramine shown below.

Etherdiamine (e is 0) Ethermonoamine Example Example Grams 37 27   40838 28 1,596 39 29 2,144 40 30 2,450

The above ether diamines (Examples 31-40) of this invention are used toprepare tertiary amines and their derivatives.

Compounds of the Present Invention

The introduction of the ether group into the molecule together with thespecific ethyl branching introduced by using 2-pentenenitrile result ina product having superior liquidity. Liquidity is a property desirablein many applications. There are not many options available to improveliquidity. The material with the highest melting point in a series isthe fully saturated product. One way to improve liquidity is tointroduce unsaturation. This is why oleyl products with one double bondare much more liquid than stearyl products that have the same number ofcarbon atoms but no double bonds. The difficulty here is that doublebonds are susceptible to a process known as rancidity. This processbreaks the double bond and forms aldehydic components that are not onlyreactive with each other, but also have bad odor. The instability limitsthe utility of unsaturated materials in many applications. We have foundthat improved liquidity is achieved by introduction of the ether groupand the branching found in the 2-pentenenitrile. Standard ether aminesand ether diamines that are made with acrylonitrile result in linearmaterials that do not have the same degree of improved liquidity as theether amines and ether diamines that are derived from using2-pentenenitrile in place of acrylonitrile.

Additionally, the products can be formulated at higher % actives. Theintroduction of the branching allows for improved solvency, and ease offormulation for use as corrosion inhibitors, biocides, asphaltemulsifiers, fuel additives, herbicide and pesticide surfactants andadjutants.

Preparation of Tertiary Amines [Ether Diamine (d=1)] 1. Preparation ofAlkoxylated Tertiary Ether Diamine General Procedure

Step 1.

The specified amount (1 mole) of the ether diamine (Examples 31-40) ischarged into an appropriately sized autoclave. The reactor is purgedwith nitrogen. Alkylene oxide is then reacted at 130-140° C.Approximately 2 hours is required for addition of the alkylene oxide.The reaction mixture is held at 130-140° C. for 2 hours, with stirring.Cool to 70° C. then vent for 10 minutes. Then vacuum strip at 15 to 28inches of mercury for 30 minutes. The product is low mole alkoxylateddiamine.

Step 2.

To the product from the first step was added 0.2 to 0.5% by weight of45% potassium hydroxide (based upon the total batch weight). By usingboth vacuum and nitrogen stripping the water level was brought down tobelow 0.1% by weight. The autoclave was then closed and heated to 110 to115° C. The specified amount of alkylene oxide (ethylene oxide,propylene oxide, butylene oxide, or combinations thereof) is then addedat a rate of one mole per hour. Once all the alkylene oxide has beenadded the batch is held at constant temperature for two hours. Theproduct is cooled down to 70° C. and vacuum strip at 15 to 28 inches ofmercury for thirty minutes. The product is then filtered. The product isthe alkoxylated diamine with the required number of moles of alkyleneoxide.

EXAMPLES 41-50

Alkoxylated Ether Diamine Ethylene Propylene Tertiary Diamine CompoundOxide Oxide Example Example Grams Grams Grams 41 31 361.0 220.0   0.0 4232 525.0 0.0 116.0 43 33 305.0 88.0    00 44 34 329.0 2,640.0     0.0 4535 375.0 0.0 116.0 46 36 406.0 88.0   0.0 47 37 465.0 0.0 1,160.0   4838 1,653.0   440.0  580.0 49 39 2,201.0   44.0  116.0 50 40 2,507.0  0.0 116.0

The tertiary amine compounds so prepared are referred to herein asalkoxylated tertiary ether diamines and conform to the followingstructure:

R¹ is selected from the group consisting of alkyl having 3 to 22 carbonatoms, aryl having 6 to 20 carbon atoms;

R² is —(CH₂CH₂O)_(a)—(CH₂CH(CH₃)O)_(b)—CH₂CH(CH₂CH₃)O)_(c)—;

a, b and c are independently integers ranging from 0 to 30, with theprovision that a+b+c are a minimum of 0 and a maximum of 60;

R³ is

d is 1;

e is 0 or 1;

x, y and z are integers each ranging from 0 to 30 with the provisionthat x+y+z is a minimum of 2 and a maximum of 60.

1. Preparation of Trimethyl Ether Diamine General Procedure

In a suitably sized autoclave is charged (1 mole) of the specifieddiamine (examples 31-40) and 0.5% by weight (based upon the weight ofthe diamine) of a nickel catalyst G-49-B. Next add 0.5% by weight (basedupon the weight of the diamine) of filter aid. Next ad 0.5% by weight(based upon the weight of the formalin) of NaH₂PO₄. The contents of theautoclave are then heated to 150° C. Hydrogen is then applied to apressure of 100 psig, with continuous hydrogen flow and continuoushydrogen venting. Next, 3.1 moles of formaldehyde (96.0 grams) is addedas Formalin (37% formaldehyde) at a rate of 0.85 ml per minute. Afterthe addition is complete, the batch is held for 30 minutes. The reactionmass is cooled to 80° C. and vented to atmospheric pressure. The productis the filtered as it is discharged from the autoclave. The product isthe desired trimethyl tertiary ether diamine.

EXAMPLE 51-60

Trimethyl Tertiary Ether Diamine Ether Diamine Compound Example ExampleGrams 51 31 360.0 52 32 525.0 53 33 305.0 54 34 329.0 55 35 375.0 56 36408.0 57 37 465.0 58 38 1,653.0   59 39 2,201.0   60 40 2,507.0  

The tertiary amine compounds so prepared are referred to herein asmethylated tertiary ether diamines and conform to the followingstructure:

R¹ is selected from the group consisting of alkyl having 3 to 22 carbonatoms, aryl having 6 to 20 carbon atoms;

R² is —(CH₂CH₂O)_(a)—(CH₂CH(CH₃)O)_(b)—(CH₂CH(CH₂CH₃)O)_(c)—;

a, b and c are independently integers ranging from 0 to 30, with theprovision that a+b+c are a minimum of 0 and a maximum of 60;

R³

d is 1;

e is 0 or 1.

Preparation of Tertiary Diamine Derivatives 1. Preparation of MethylChloride Quaternary Compound General Procedure

In a stainless Parr autoclave was added one mole of tertiary amine(examples 41, 46, 51, 56) 1% sodium bicarbonate (based upon the weightof the tertiary amine), and isopropanol (based upon the desired activityand viscosity). The autoclave is sealed, agitation applied and anitrogen purge applied. The temperature is raised to 85° C. Charge 2.25moles (114.8 grams) of methyl chloride slowly, so that the temperatureis maintained between 80° C. and 90° C. After all the methyl chloride isadded, keep the temperature at 80° C. for two hours under agitation.Cool down and filter. The product is used without additionalpurification.

Methyl Chloride Quat Tertiary Diamine Isopropanol Example Example GramsGrams 61 41 581.0 228.0 66 46 494.0 200.0 71 51 402.0 168.0 76 56 550.0217.0

1. Preparation of Methyl Sulfate Quaternary Compound Procedure

In a 4 necked flask containing a thermometer, mechanical stirrer,condenser and dropping funnel was added 1 mole of tertiary amine(examples 42, 47, 52, 57) and isopropanol (based upon the desiredactivity of the final quaternary compound) and 3% water (based upon thetertiary amine weight). The contents were heated with stirring to 70° C.while adding 2.17 moles of dimethylsulfate (283.5 grams) from thedropping funnel over 1 hour. The mixture was stirred at 70° C. for 1 ourafter the addition was complete. The desired pentylammoniummethylsulfate compound was cooled and filtered.

Methyl Sulfate Quat Tertiary Diamine Isopropanol Example Example GramsGrams 62 42 641.0 298.0 67 47 1,625.0   626.0 72 52 567.0 278.0 77 57507.0 253.0

1. Preparation of Amine Oxide Procedure

In a four necked flask equipped with a stirrer, dropping funnel, and athermometer, is added 1.0 mole of the specified tertiary amine (examples44, 49, 54, 59). Next is added isopropanol to make the desired activityand viscosity of the amine oxide. The mixture was stirred and slowlyheated. 229.5 grams of 35% hydrogen peroxide (2.37 moles of H₂O₂) isadded dropwise keeping the temperature between 55° C. and 65° C. Therate of addition is determined by the exotherm, keeping the temperatureof the reaction in the specified range. After the addition, the reactionwas held to 60° C.-65° C. for 2 hours. The amine oxide is obtained andutilized without purification.

Amine Oxide Tertiary Diamine Isopropanol Example Example Grams Grams 6444 2,961.0 2,847.0 69 49 2,361.0 2,242.0 74 54   371.0   253.0 79 592,243.0 2,125.0

1. Preparation of Benzyl Chloride Quaternary Compound General Procedure

In a four neck flask equipped with a thermometer, condenser, droppingfunnel and mechanical stirred was added one mole of tertiary amine(examples 43, 48, 53, 58). Next add, 1% by weight of sodium bicarbonate(based upon the weight of the tertiary amine), 3% by weight (based uponthe weight of the tertiary amine), and isopropanol (based upon thedesired activity and viscosity of the final quaternary compound). Stirand heat to 80° C.-85° C., under a nitrogen blanket. Add 2.25 moles ofbenzyl chloride (285.8 grams), while maintaining the temperature in therange of 80° C.-85° C. After the addition is complete, hold the contentsat 80° C.-85° C. for two hours. Cool the contents and filter. Theproduct is used without additional purification.

Benzyl Chloride Quat Tertiary Diamine Isopropanol Example Example GramsGrams 63 43 393.0 216.0 68 48 2,673.0 976.0 73 53 347.0 201.0 78 581,695.0 650.0

The compounds of the present invention are outstanding surface activeagents, providing outstanding emulsification, detergency and foamingproperties. By the proper selection the surfactants of the presentinvention can be oil, or water soluble, and be used to make oil inwater, or water in oil emulsions. The branching gives better liquidity,making the compounds useful in cold emulsification processes. Inaddition the compounds of the present invention emulsify greaterquantities of oil than do conventional surfactants.

What is claimed:
 1. An ether diamine quaternary conforming to thefollowing structure:

wherein: R¹ is selected from the group consisting of alkyl having 3 to22 carbon atoms, R² is—(CH₂CH₂O)_(a)—(CH₂CH(CH₃)O)_(b)—(CH₂CH(CH₂CH₃)O)_(c)—; a, b and c areindependent integers ranging from 0 to 30; R³ is

d is 1; e is 0 or 1; R⁴ and R⁵ are selected from the group consisting of—CH₃; and —CH₂CH₂O)_(x)—(CH₂CH(CH₃)O)_(y)—(CH₂CH(CH₂CH₃)O)_(z)H; x, yand z are independent integers ranging from 0 to 20, with the provisionthat x+y+z is greater than or equal to 3; R⁶ is selected from the groupconsisting of —CH₃ and —CH₂—C₆ H₆; M is an appropriate anion needed forcharge balance and is selected from the group consisting of Cl, Br, andCH₃SO₄.
 2. An ether diamine quaternary of claim 1 wherein R¹ is C₃H₇, bis 5, R⁴, R⁵and R⁶ are CH₃ and M is CH₃SO₄, and e is 1.